Dehydrogenation of hydrocarbons



Aug. 16, 1938. v R. ROSEN 2,125,817

' DEHYDROGENATION 0F HYDROCARBONS Filed June 3, 1936 REACTION WA rez SEPAPA-roa e CHAMER n 5 n f5 VEASEL @L4M/am am i Patented 16, 1938 UNITED STATES DEHYDROGENATION F HYDROCARBONS Raphael Rosen, Elizabeth, N. J., assignor to Standard Oil Development Company, a corporation oi' Delaware Application June 3, 1936, serial No. 83,264

11 Claims.

The present invention 'relates to the productinl of unsaturated hydrocarbons from those of a. more saturated nature, and is particularly directed to an improved method for accomplishing this result. More specifically, the present 1nvention provides for the dehydrogenation of hy- `drocarbon material in the presence of a catalyst and of an addition agent having a tendency to influence the equilibrium of the reaction in the direction of the formation of larger quantities of unsaturates.

Recently the problem of dehydrogenating hydrocarbons has become intensied by the development of numerous processes for the produc- 4tion of synthetic gasoline from low ymolecular weight oleiins, such as propylene and butylenes. These hydrocarbons do not existkas such, in high concentrations in any available source but must be obtained by the dehydrogenation of saturated refinery gases or natural gases, or light gasolines containing butane and propane.v Therefore, theV practicability of those processes for theproduction of synthetic gasoline, which require olefins as a starting material, is dependent, to a large 'extent-upon the cost of converting the saturated hydrocarbons into olefins. V

The catalytic dehydrogenation of parain hydrocarbons is a well explored eld of research. Most of the developments in this liield, however, 'have been in the discovery of suitable catalysts. Among the more common catalysts developed for this type of reaction have been the catalysts described in Patent No. 1,913,940 containing an oxide of a metal of Group VI of the periodic system alone or mixed with other difiicultly reduc- ,ible oxides, such as alumina, active charcoal, active silica, lustrous carbon, aluminum borate, the catalysts described in Patent No. 1,913,941, meta-phosphates, and many others of a similar nature. In the process of the present invention any of these well known dehydrogenation catalysts may be employed.

According to the present invention the yield per pass of unsaturates, obtainable by dehydro-v (Cl. ISG- 10) oxidize the hydrocarbons present to oxygenated organic compounds.

Because of its relative cheapness, non-corrosive properties, and greater effectiveness, sulfur dioxide is much to be preferred for the purpose of the present invention. Investigation has indicated that by using suicient sulfur dioxide and a proper temperature, a very high conversion of the initial material to the desired unsaturates is possible.

It is not clearly understood what function the gaseous oxide plays. It may be assumed that in some cases it reacts with the hydrogen produced by dehydrogenation, thereby eliminating this hydrogen and shifting the equilibrium of the reac 15 tion toward the formation of larger amounts of the desired unsaturates. By reason ofthe fact, however, that hydrocarbons can be dehydrogenated by the action of sulfur dioxide below temp'eratures which are normally suitable for dehy-l drogenation of these hydrocarbons, there is reason to believe that at least in these cases the sulfur dioxide reacts directly with the hydrocarbon, especially if the hydrocarbon contains a tertiary carbon atom. 25

The data published by Frey and Hupke, in Industrial 8a Engineering Chemistry, vol. 25, page 54, 1933, on the equilibrium composition of gases from the dehydrogenation of isobutane show that at `temperatures as low as 300 C. some conversion of isobutane into isobutylene and hydrogen is possible. The composition of the reaction mixture at this temperature appears to reach equilibrium when it contains about 98% isobutane and about 2.0% of isobutylene and hydrogen. When one of the gaseous oxides, employed according to the present invention, is present, it reacts with this hydrogen, thereby destroying the equilibrium and making possible a further conversion of the isobutane to isobutylene.

The reactions which presumably occur are as follows:

of the hydrocarbon, particularly with a hydrogen attached'to a tertiary carbon atom. This conclusion is strengthened by the fact that the conversion of hydrocarbons to less saturated hydrocarbons can be effected at temperatures much below that at which a thermal splitting oif of hydrogen will occur. Even at temperatures as low as 300 F. a noticeable dehydrogenation of the hydrocarbon undergoing treatment occurs. Thus, according to the present invention, there is contemplated not only the employment of one of these gaseous oxides in the catalytic dehydrogenation of hydrocarbons but in the dehydrogenation of these hydrocarbons in the presence of contact masses which are not dehydrogenation catalysts and in the absence of any contact mass.

The amount of sulfur dioxide to be added to the initial material for the dehydrogenation may vary within wide limits. In general, the greater the quantity of sulfur.y dioxide added the greater will be the conversion per pass of the initial material to less saturated hydrocarbons. The upper limit of the amount of gaseous oxide added is, of course, that determined by the economic balance between the extent of conversion desired and a practicable capacity of the reaction chamber, it

being apparent that the greater the amount of SO2 employed the less will be the capacity of the reaction chamber for the desired reaction. Indications are, however, that, by suitably adjusting the'amount of SO2 employed, conversions of the hydrocarbons, per pass, higher than those attainable by hitherto known methods, can be obtained without decreasing the capacity of the reaction chamber below commercial requirements. Usually it is desirable to employ an amount of SO2 exceeding the amount theoretically required to react with the evolved hydrogen by from .10 t0 In general, the conditions to be employed when a dehydrogenation catalyst'is used are substantially the same as those employed in the absence of sulfur dioxide. Due to the effect of the sulfur dioxide on the equilibrium of the reaction, how# ever, it is possible, if desired, to operate in the presence of sulfur dioxide at temperatures from 150 to 300 F. below that required for a corresponding dehydrogenation in the absence of sulfur dioxide. Accordingly, as a result of the present invention, the temperature range of from about 900 F. to 1150 F., ordinarily employed for catalytic dehydrogenation, is expanded to a lower temperature limit of about 650 F.

The process of the present invention is usually conducted at atmospheric pressure. As indicated above, reduced pressure may be employed. When the dehydrogenation is conducted as a preliminary step to polymerization, as is usually the case, it is very advantageous to 4carry out the dehydrogenation under pressure, since it is much more economical to develop the pressure necessary for polymerization, usually not in excess of 600 lbs. per square inch, by applying at least part of the pressure to the initial material for the dehydrogenation, on which pressure may be built up while said material is in the liquid phase, than by applying all the pressure to the vaporous products of the dehydrogenation. Since dehydrogenation is usually accompanied by an increase in volume, however, it is not to be expected that it would be favored by pressure. Accordingly the practice in the art has been to conduct the dehydrogenation at atmospheric pressure.

According to the present invention, the dehysulfur dioxide reacts directly with the hydrogen drogenation occurs without any appreciable increase in volume of the primary reactants, namely, hydrocarbon and hydrogen. Altho the volumetric quantities of products produced theoretically exceeds those of the initial materials, it is to be remembered that the hydrogen produced is removed from the reaction. Consequently, th eiect of pressure, which would normally tend to reverse the dehydrogenation reaction, is eliminated. Therefore, the dehydrogenation, according to the present invention, may be carried out under any desired elevated pressure without any substantial loss in efiiciency.

As previously indicated, the dehydrogenation oi' Ca and C4 hydrocarbons is usually conducted for the purpose of providing an initial material for the production of synthetic gasoline by polymerization. Since the presence of hydrogen in substantial amounts has been found to be undesirable in polymerizations of this type. it has been the practice to separate the oleilns from the hydrogen before subjecting the oleiins to apolymerization. This separation step constitutes a very substantial item in the cost of producing gasoline from C: and C4 saturated hydrocarbons.

By the present invention 'the combination of dehydrogenation and polymerization has been greatly improved by reason of the fact that when sulfur dioxide is employed in the required amount no free hydrogen is contained in the reaction product. The free sulfur and hydrogen sulde, which are contained in the reaction product, are much more readily removable than free hydrogen. A specific embodiment of the present invention, therefore, is the dehydrogenation of C: and C4. hydrocarbons in the presence of a catalyst and sulfur dioxide, followed by the condensation of sulfur and the removal of hydrogen sulde by washing with high boiling alkylolamines or alkali metal salts of phenols, or any other suitable solvent, and then by polymerization of the olens.

Alternatively, the hydrogen sulfide may be removed from the reaction products from the dehydrogenation zone while they arestill hot by contacting them with luxmass (hydrated iron oxide), or any other contact mass containing a metal oxide which will react with hydrogen sulfide, and sulfur may then be removed by condensation.

Where the hydrogen sulilde is removed by reaction with a metal oxide, it will also be advantageous to precede the polymerization by any suitable expedient for the removal of water. These purification steps result in a reduction in the temperature of the olefins, which is necessary in any case where the polymerization is of the catalytic type, particularly where it is eiIected by sulfuric acid or phosphoric acid at temperatures not exceeding 250 C. Itis to be understood, however, that the polymerization may also be eected simply by subjecting the oleiins to a relatively high temperature and a high pressure in the known manner. Such a polymerization is usually conducted under a pressure considerably in excess of 500 lbs. per square inch, such as 1000 lbs. per square inch, and at a tempera` ture between 600 and 900 F.

The removal of sulfur dioxide from the reaction product is not necessary since sulfur dioxide has no detrimental eilect on the polymerization. especially where it is eifected by sulfuric or phosphoric acid. If it be desired to remove the sulfur dioxide, however, this may be readily accom-l plished by scrubbing the reaction products with a mixture oi' aromatic amines, such as xylidine or toluidine and water, or by scrubbing with sodium thiosul'tate solution, or with alkylolamines or phenates.

Another application of the present invention is the formation oi' dioleilns. from oletlns or from paramns. Ordinarily, in the dehydrogenation of parailins. the quantity of sulfur dioxide to be employed may vary from about one-tenth of a mole to 1/2 a mole of sulfur dioxide per mole of hydrocarbon. With greater amounts of sulfur dioxide the oleins formed tend to become more unsaturated to form dioleiins. Due to the stronger bond between hydrogen and carbon in diolefins, however, it is preferable to rst form the oletlns and then to convert the oleiins to dioleiins at a higher temperature but at much higher thruputs or lower contact times. Usually the conversion to dioleiins is effected at atemperature about `200 F. above the temperature employed for Vthe production of the olefins. A temperature between l0001200 F. should be selected for the production of dioleiins from olefins.

The reaction products of such a conversion should be immediately quenched to a temperature below about 500 F.so as to avoid losses of the diolens.-

A further application of the present invention is in the production of acetylene from methane or ethylene and in the production of ethylene from ethane. Many thermal processes for the conversion of methane to acetylene and ethylene at temperatures of at least 1832 F. are known. The addition of substantial quantities of sulfur dioxide to the methane increases the yield of acetylene at temperatures above 1832F. and permits the production of substantial quantities oi ethylene at temperatures between about 1300 and 1600 F. .By increasing the time of treatment at these temperatures the yield of ethylene is decreased in favor oi the production of acetylene. When ethylene is used as the initial mate-` rial at these temperatures satisfactory yields of acetylene are obtained.

In the accompanying drawing a front elevation of a plant, suitable for carrying out the present invention, is illustrated in diagrammatic form. Referring to the drawing, l is a feed line for hydrocarbons to be dehydrogenated, 2 is a compressor which may be employed in the event that the dehydrogenation is to be conducted under pressure, 3 is an inlet line for sulfur dioxide, 4 is a reaction chamber containing a dehydrogenation catalyst b, 8 is a conduit for conducting the reaction products from chamber 4 to a condenser l from which said products are discharged. into a separating vessel in the bottom of which any sulfur formed and the oleilns, ii' they be of suiliciently high molecular weight, are deposited and from which they may be drawn off thru lines 9 andu i0 respectively.

lit is desirable to convert any hydrogen suliid contained in the reaction products from chamber t into sulfur so as to facilitate the separation of all sulfur from these reaction products. To this end it is often desirable to add -a quantity o sulfur dioxide and a relatively small amount of water vapor to the reaction products issuing from chamber l thru line 25. Whenl this expedient is adopted it will be desirable to provide suiilcient time for the reaction between sulfur dioxide and hydrogen suliide by interposing a chamber in the nature of a soaking drum between reaction chamber 4 and condenser l, or to make the coil in condenser 1 of sufllcient length to provide an adequate period of time for this reaction.

'Separator 8 may be provided with internal construction, such as baille plates, or discs and doughnuts, Ii, and with an inlet Il for a solvent for hydrogen sulilde. It a solvent is not employed and the oleflns produced are of low molecular weight. such as propylene and butylene, they are conducted thru line il thru a chamber i4 packed with a contact mass, such as luxmass, which removes hydrogen sultlde. II a solvent;4 for hydrogen sulilde has been employed in chamber 8, the oleilns are bypassed around chamber I4 by conduit I 6.

The vapors issuing from chamber f I4 or from chamber 8, as the case may be, pass thru a water separator Il which may be lled with cooling coils for the condensation of the water, or may be packed with a dehydrating agent of any common type. The dried vapors are then conducted thru line I8 to a suitable receiver, or in the case of oleflns, such as propylene and butylene, to a polymerization chamber I9 which may contain a body of sulfuric acid 20, or may be packed with clay or a phosphoric acid catalyst, or any other suitable polymerization catalyst. The chamber IS may also be free from any catalyst if polymerization is to be effected by the conjoint action of temperature and pressure. A suitable'outlet may be provided in chamber i9 for the withdrawal oi' any liquid polymer which may collect therein. The vaporous products issuing from I9 pass to a fractionating tower 2i from which liquid prode ucts are drawn off thru line 22 and vapors and gases which may be colnposed of unconverted initial material from tower 4, some unpolymerized oleflns, and in certain instances some sulfur dioxide, are drawn oil thru line 23. When such gases -or vapors contain a substantial percentage 4of unsaturates, it 'may be advantageous to pass them again into line i8 thru line 2t. Otherwise they are recycled to reaction chamber 4.

Various modifications may be made in the apparatus shown in order to adapt it to the particular process involved. For example when the process involved is the production of acetylene either from ethylene or from methane, the reaction chamber 4 is preferably followed immediately by a quenching zone. In case the hydrogen suliide is washed out of the dehydrogenation product, in a process in which the olefins produced are polymerized and then hydrogenated, it may be desirable to recover the hydrogen sulfide from the wash liquid, react it with a metal or with oxygen for the production of hydrogen, and use the hydrogen so produced for the hydrogenation of the polymer.

The following results of trial experiments indicate qualitatively the nature of the improvement effected by the present invention. These examples are not intended to set forth the ideal working conditions, but are simply described to demonstrate the manner in which dehydrogenation is effected under any given set of conditions by the addition of SO2 to the feed stock.

Example 1 Cr (NO3) 39H20 and 250 grams of stoneware. The composition of 4 the feed mixture and the rate of flow of the mix'- ture were so adjusted that 94 volumes of isobutane and 40 volumes of SO2 per volume of catalyst per hour were fed through the reaction chamber.

The reaction chamber was encased in a bronze block maintained at a temperature of 1010 F.

A sample of the product taken after 11/2 hours on stream contained 12.1% hydrogen, 1.6% CO, 0.9% CH4, 0.3% Cz hydrocarbons, 62.2% isobutane and 22.9% isobutylene. 27% of the initial isobutane reacted and the efficiency of the reaction, i. e., the amount of reacted isobutane which was converted to isobutylene was 98%.

Example 2 After the reaction'described in Example 1 had been on stream about three hours the feed rate was changed to 102 volumes of isobutane and 40 volumes of SO2 per volume of catalyst per hour. At the end of four hours a sample of the product was found to contain no hydrogen, 1.1% (70,03% Cz hydrocarbons, 74.4% of isobutane and 24.2% of isobutylene. 25% of the initial isobutane reacted and the eiilciency of the reaction was 98%.

Example 3 At the end o! the fourth hour in the run described above the feed rate was changed to 46 volumes of isobutane and 40 volumes of SO2 per volume of catalyst per hour. A. sample of the product taken at the end of the fifth hour contained 0.2% hydrogen, 0.1% CO, 0.9% CH4. 1.1% C2 hydrocarbons, 0.5% C: hydrocarbons, 54.1% isobutane and 43.1% isobutylene. 43+% of the initial isobutane reacted with an eillciency of 99+%.

' Example 4 Example 5 A run, similar in all respects to the previous run except that no sulfur dioxide was added, was conducted with a feed rate of 83.2 volumes of isobutane per volume of catalyst per hour and a. block temperature of 1010 F. At the end of the fourth hour a sample of the product contained 15.8% hydrogen, 1.8% CH4, .4% C2 hydrocarbons,

.1% C3 hydrocarbons, 63.5% isobutane and 18.4% isobutylene. 22.5% of the initial isobutane reacted with an eiliciency of 95%. Comparing these results with the results obtained in Example 2, it is seen that, although in the latter case the feed rate was much hmher, the per cent reacting and the efficiency of the reaction was also greater. More important,.however, is the fact that in the latter case the reaction product was free from' hydrogen, indicating that the SO2 had eliminated the hy'drogen and had inuenced the equilibrium to the production of greater amounts of isobutylene.

Example 6 Isobutane was passed at 1040 F. over a catalyticaliy inactive stoneware at the rate of 1.0 cu. ft./hr./340 cc. of stoneware. There was no volume increase and the percentage of unsaturates in the exit gas was 0.9%.

SO2 was then mixed with the feed in a proportion of one volume of SO: for three volumes of A mixture of isobutane and SO2 was passed at a rate 'corresponding to 1.0 cu. ft./hr. of isobutane and .38 cu. ft./hr. of SO2 over 340 ce. of pumice stone at 1040 F. There was no increase in volume. The exit gas contained 9.0% of unsaturates. The SO2 was then omitted from the feed, the flow of isobutane remaining unchanged. The content of unsaturates in the reaction product dropped to 2.0% and the volume of the reaction gas increased to. 1.02.

In the above examples, in which sulfur dioxide was employed, the sample of the product was analyzed only after being scrubbed with caustic for the removal of sulfur compounds. It is also to be noted that the relatively high percentage n of hydrogen in the sample described in Example l is attributable to the fact that the reaction unit had not yet been brought to reaction conditions. It usually requires from two to three hours to adjust all the factors involved, such as feed rate and temperature, to a point where uniform results are obtainable.

It is noted that the product always contains a large percentage of isobutane. In practice it is customary to contact this product directly with sulfuric acid at suitable conditions to convert the isobutylene into higher boiling polymers and to recycle the isobutane from the polymerization unit to the dehydrogenation unit. In this procedure it is permissible to pass the whole reaction product from the dehydrogenation unit through the polymerization unit and to recycle the sulfur compounds, such as sulfur dioxide, back to the dehydrogenation unit with the isobutane. The use of sulfur dioxide in the dehydrogenation makes this combination of steps much more desirable than would be the case with a combination of ordinary catalytic dehydrogenation and polymerization because in the latter case hydrogen builds up in the recycled gases to such an extent as to greatly reduce the eiliciency of the dehydrogenation step whereby it is usually necessary to include between the polymerization step and the dehydrogenation step, equipment for eliminating hydrogen from the recycled gas, this step being accompanied by a considerable loss of energy.

The nature and the objects of the present invention having thus been described and its advantages experimentally illustrated, what is claimed as new and useful and desired to be secured by Letters Patent is:

l. In the catalytic dehydrogenation of hydrocarbons at temperatures in excess of about'650 F., the step which comprises contacting said hydrocarbons with a catalyst in the presence of an oxide of sulfur. i

2. A process for the conversion of isobutane to isobutylene which comprises passing a mixture of isobutane and sulfur dioxide over a dehydrogenation catalyst at a temperature between about 650" F. and 1150 F.

3. A process for the conversion of isobutanel into liquid polymers of the gasoline boiling range which comprises passing a mixture of isobutane and sulfur dioxide over a dehydrogenation catalyst, contacting the resulting products with a catalyst capable of polymerizing isobutylene at a suitable polymerization temperature whereby true liquid polymers are formed, separating the liquid polymers from the lreaction mixture leav-i ing the polymerization zone and recycling the remainder of said reaction mixture to the dehydrogenation zone.

4. A process according to the preceding claim in which the reaction mixture leaving the dehydrogenation zone is subjected to a treatment for the removal of sulfur and its compounds prior to;

being introduced into the polymerization zone.

5. A process according to claim 3 in which sulfur dioxide and steam are added to the reaction mixture leaving the dehydrogenation zone, and the resulting mixture is maintained under suitable conditions for a suitable period to effect a reaction between the sulfur dioxide and any hydrogen sulfide in said reaction mixture to form sulfur, and the sulfur so produced is removed from the reaction mixture by condensation prior to the introduction of said reaction mixture into the polymerization zone.

6. A process for the conversion of a normally gaseous parailin into the corresponding olen which comprises passing a mixture of said parafiln and sulfur dioxide into contact with a dehydrogenation catalyst at a temperature suitable for the conversion, contacting the reaction mixcatalyst vis composed of a mixture of chromicl oxide and alumina deposited on porous stoneware. Y

10. A process according to claim 6 in which the temperature employed is between 900 F. and 1100 F.

11. A process for converting a hydrocarbon into a less saturated hydrocarbon which comprises subjecting a mixture of said hydrocarbon and an oxide of sulfur to a temperature sutil-` ciently high to split oif hydrogen from said hydrocarbon, said temperature being at least 650 F. and being higher the lower the molecular weight of the initial hydrocarbon material.

RAPHAEL ROSEN. 

